Decontamination of uranium



Feb. 4 1958 H. M. FEDER ETAL DECONTAMINATION- OF URANIUM Filed Feb. 21, 195e INVENTORS l 2,822,260 DECONTAMINATION F URANIUM Harold M. Feder, Park Forest, and Norman R. Chellew,

Joliet, lll., assignors to the United States of America as represented by the United Statesl Atomic Energy Commission Application February 21, 1956, Serial No. 574,051 9 Claims. (Cl. 75-84.1)

This invention deals with the separation of rare earth and other fission product metal values from neutronbombarded uranium and also with the separation of rare earth metal values from uranium broadly.

In the processing of neutron-bombarded uranium it is desirable to recover the uranium for re-use without dissolving it or otherwise diluting the metal. For many uses it is furthermore advantageous to obtain a plutoniumenriched uranium-base fuel material; this is true, for instance, if the uranium is to be used as fuel for a power breeder reactor.

It is an object of this invention to provide a process for the removal of fission products from neutron-bombarded uranium in which the uranium is not diluted.

It is another object of this invention to provide a process for the removal of fission products from neutronbombarded uranium in which the uranium remains in its metallic state.

It is also an object of this invention to provide a process for the removal of fission products from neutronbombarded uranium in which the fission products are removed in a comparatively concentrated form which facilitates their disposal.

It is still another object of this invention to provide a process for the removal of fission products from neutronbombarded uranium in which the ssion products are extracted to a high degree but the plutonium is retained in the uranium.

These objects are accomplished by melting the uranium in contact with at least one oxide selected from the group consisting of thorium oxide, magnesium oxide, aluminum oxide, beryllium, oxide, and uranium dioxide. The melting is preferably carried out at from 1150 to 1400* C. in an inert atmosphere, such as argon or helium. The heating time depends on the temperature and the size of the batch; a period of 4 hours was found satisfactory in a great many instances. During this treatment a scale of uranium dioxide forms on the uranium, as was ascertained by X-ray diffraction, which is strongly concentrated in regard to most of the fission products.

From the thermodynamic point of view the oxidation of appreciable amounts of uranium by the oxides with which the uranium is contacted in accordance with this invention was quite unexpected, as is obvious from Table I which gives free energy values of formation of some of the oxides in kilocalories per gram-atom of oxygen (-AF). These energy values, of course, must be modified to consider surface energy values and also to take in account abnormalities occurring in solutions of various oxides.

TABLE I Oxide -AFI at nite States Patent O ICC C. At this temperature the oxide dross or slag which contains the ssion prodducts remains solid, and the molten uranium can be separated therefrom directly.

The crucibles can be made by dry-pressing, slip-casting, or any other method known to those skilled in the art. In the case of using uranium dioxide as the crucible material it is advantageous to tire the formed crucible in an atmosphere of purified hydrogen at approximately 1750 C.

In order to carry out the process of this invention the irradiated fuel elements or slugs are rst decanned and then surface-treated by methods known to those skilled in the art for the removal of any bonding material. For each experiment reported in this specification two disks were cut at symmetric locations from a slug thus treated. One of the two disks was analyzed without treatment as a control sample; the other disk was treated by the process of this invention.

That disk was prepared for the melting operation according to this invention by pickling it with nitric acid and then drying. The crucible made of one of the oxides listed above was degassed at a temperature of at least 1000 C. and then permitted to cool in vacuum or au inert atmosphere, such as helium. The disk was then placed into the crucible and both together were then de-A gassed in an electrical furnace at 600 C. to a pressure of about 10-4 mm. of mercury.

Helium of about 1.1 atm. abs. was introduced to the system and then continuously passed therethrough at to cc./min.; at the same time the temperature was increased to about 1200 C. and maintained for a predetermined time. Instead of sparging with helium a stationary helium atmosphere was also found satisfactory.

After the metal had been held at the temperature for the time desired, the electrical power was shut ol and the charge was allowed to cool in the helium atmosphere. The melts were not removed until the temperature had reached 150 C. or below. It took about 24 hours until the content of the crucible had cooled down to approximately 100 C.

In the embodiment using an oxide crucible of conventional construction the uranium obtained was covered with a skin of oxide. This skin was dissolved separately from the interior or ingot of uranium by chemical means for the purpose of analysis as will be described below.

In some runs an oxide crucible was used that had a hole in the bottom; a stopper fitted into the hole and was operated by a rod attached to the stopper. As soon as the melting operation was completed, the stopper was raised so that the molten metal was cast through the bottom into a tantalum crucible, for instance, arranged underneath. An average of about 2% of the entire mass was retained in the oxide crucible as a skull. This skull, like the oxide skin described above, was enriched in lission products, as will be shown later.

Another arrangement which was used successfully is diagrammatically illustrated in the accompanying drawings, Figure 1 being a sectional view of the device in melting position and Figure 2 a similar view in metal-slagseparating position.

The arrangement comprised two concentrically arranged crucibles, an inner oxide crucible 3 with a bottom hole 4 and an outer aluminum oxide crucible 5 which are lapped together for a smooth fit. The uranium was melted in the inner crucible 3 while it was supported by the outer crucible 5. f When the liquation was finished, the inner oxide crucible 3 was slightly lifted, as shown in Figure 2, so that the molten metal could run out of the inner crucible 3 through the hole 4 into the outer crucible 5; the skull was retained in the inner crucible 3. This arrangement is particularly advantageous in the case that operation by remote control is necessary.

The process can be carried out in any type of equipment known to those skilled in the art; for instance, the oxide crucible with the uranium was placed into a porcelain tube which was then inserted into an electrical ing) times on semilogarithmic paper. Smooth curves were drawn through the points of these plots, and the curves were used as a basis of comparison. The slopes of the curves coincide with the known half-lives. The

resistance furnace. The whole assembly was installed in 5 radiochemical analyses of the treated materials could then a ventilated hood and the furnace was surrounded by steel be compared with interpolated values for the controls in shielding. The crucibles in the porcelain tube were in order to eliminate the variation due to decay time between the center ofthe furnace-heating zone. The melt temper# analyses. Separate cerium analyses were not always made atures of 1200 C. were attained in approximately one because the total rare earths activity was found to parallel hour with an input of two to three kw. Meansfor 'evacua- I0 the ceriurn144 in behavior. tion and for blanketing with argon or helium gas were In the following some examples are given. In these connected with the system. experiments, the uranium was melted in crucibles made of VFor analyzing the melted or treated disk and the unthe various oxides. The skin and ingots were dissolved treated control disk, they were dissolved separately in separately as described above, and the solutions were nitric acid or a hydrochloric acid-nitric acid mixture, and l5 analyzed. The contents of the various solutions in uraeach solution was analyzed. The skin or skull sections, as iiium, plutonium and various typical fission products are the case may be, which contained the oxide slag and the given in each example in percent by weight of their amount uranium metal ingot were also dissolved separately in each in the starting material. It will be noted that in many instance. In SOI'fie Cases the Skin Sections On the top Of the instances these percentage Values d0 not add up to 1GO; ingot or on the bottom and on the sides were dissolved 20 apart from minor errors due to analytical methods, etc., Sepafaieiy; ibis WHS aCCOmPiiSbed by Painting ib@ Surface most of the discrepancies were found to be caused by t0 be Protected With a beDZbHS Solution 0f Wax iiniig volatilization and/ or diffusion of thcse fission products of the nonprotected area was then carried out with nitric into the Crucible, acid, preferably of a concentration between 4 N and 8 N Example 1 at .tempratures not hlgner than-20o below/.the memlig 20 A disk of neutron-irradiated uranium weighing 70.5 g., paint 0I the Wax' Where au 5,1des OI th? 5km were dis." after cooling for 265 days, was found to contain 7 g. of solved together, the ingot was immersedin the acid .until plutonium Per ton This disk was melted in a funnel a clean metal st irtace free from dark oxide was obtained. Shaped Urania Crucible at 12000 C for 4 hours. After iter this Skinning step the remaining metal was dissolved 30 Cooling of the melt the iugm Obtained was Cut vrticauy in boiling nitric acid 0f a Concefiifatioii 0f about i3 N into 3 sections, and each section was skinned individually under rellux. The linal concentrations of both skin and with dilute nitric acid, The various contents 0f the ininterior solutions were usually between about 6 N and 8 N. terior and of the skin of each section are shown in Table II.

TABLE II Section Ura- Pluto- Rare Ce Sr Ru Cs Te Nb Zr Total Total'y nium nium Eartlis Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Top section, skin. 4.1 6.0 69. 9 59. 5 s6. 3 41. s3. 3 12.5 67.1 63. s 2s. 0 Top section, interior.- 55. 0 49. 6 0. 5 0. 2 0. 9 38. 2 1. 7 5. 4 49. 5 21.0 6. 4 43. 4 Middie section, skin 0. s 1. 7 11.0 10.7 4. 2 o. 4 3. 6 5. 4 1. 6 5. 4 s. 5 2. 7 Middle section,

interior 21.9 20.2 0. 1 0. 05 0.1 20. 9 0.6 1. 5 21. 3 s. 6 4. o 16. 9 Bottom section, skin-, 2 1 2. 4 4. 2 4. 7 0.3 1.6 0.3 1. o 1. s 1.2 3. 3 1. s Bottom section,

interior i5. 7 14. 3 0. 4 0.05 0.05 15. 5 0.4 1. 0 14.7 s. 1 1. 7 12. 2

When bottom-pour methods were used no Skinning, It will be seen from this table that plutonium and ofcourse, was carried out. In these instances, the retained ruthenium are retained practically quantitatively in the slag or skull and the cast ingot in the tantaluin crucibles uranium and that niobium, While it was extracted to some were dissolved separately. n0 degree,its bulk remained in the uranium. All other iis- The rare earths, ceriurn, strontium, rutlienium, cesium, sion'product values analyzed for were predominantly exand tellurium were counted as beta activities. Zirconiuin tracted into the skin. and niobium gammas were counted through a lead absorber using a scintillation Counter which was adjusted n Example Il to discriminate against photons of less than 0.1 m. e. v. 78.4 g. of irradiated uranium which contained 7 g. energy Molybdenum was determined Colorimetrically, of plutonium perron and had been cosied for 298 days arid uranium was determined either by weighing directly was melted as described above in a thoria Crucible. The as metal or by the acetone-thiocyanate Colorimetric ingotobtained was skinned three times in succession with mCihOd Plllblium W28 fOiiOWd by means of the standnitric acid and 'each or the three solutions was analyzed. ard lanthanuin iluoride carrier technique and counting in 60 The interior was also dissolved and analyzed. The re an alpha proportional counter. sults are given in Table III.

TABLE III Section Ura- Pluto- Rare Cc Sr Ru- Cs Te Nb Zr Total Total n' muni nium Earths out... 5km Penti." PJC Pe'L mi?? P $172 Pe'c Pe' Pei-I Pe'cf Pee Periti@ Pmeff Middle skin. 0.7 1. 2 26. 7 25. 1 2e. o 0.6 14. 7 19. 7 2. 7 17.4 22.0 6. 5 Inner skin 2. 9 2. 4 16. 7 16. 5 i 7. 2 2. s 6. 7 '6.' o 2. 7 10.2 12. 9 4. 7 interior 95.5 87. 3 1. 1 `1. 3 0. 1 91. 1 3. 4 19. 4 74. 9 27. 4 9. 5 47, 4

Inorder to increase the precision of the radiochemical analyses of the controls, the fission product activities of the untreated metal were plotted versus the decay (cool 75 This experiment shows that the bulk of the ssion vproducts removed from the metal is taken up by the uranium oxide formed.

v'compiled in Table VI. It will be seen that the period of 51.8 g. of uranium containing 7 g. of plutonium per 91.4 g. of neutron-bombarded uranium cooled for" 330 ton and cooled for 306 days was melted in a magnesia da s and containin 7 of lutonium er ton was melted crucible for four hours at 1200 C., and the lngot oby g p o p tained after cooling was skinned three times in succesm a magnesla crucible at 1200 C' for 30 mmutes and Sion with nim'c acid The contents of the various frac. the metal was then allowed to cool. The ingot was skinned tions are given in Table IV. 3 times in succession as described before. The distribu- TABLE IV Section Ura- Pluto- Rare k0e Sr Ru Cs Te Nb Zr Total Total'y ntum nium Earths Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent outer skin 1.2 3.7 44.7 46.6 74.9 0.4 24.6 47.0 5.9 41.8 44.1 .4 1.1 1.8 23.3 26.1 17.6 0.6 11.9 10.0 2.7 15.5 20.5 .7 1. 9 1. 7 11.9 12. 6 6. 4 1. 6 5. 6 3. 6 2. 7 8. 9 10.3 4. 9 95.5 88.0 1.7 1.9 1.6 85.1 2.7 39.8 74.3 24.7 9.9 64.8

Example IV o tion of the ssion products in the various solutions is `45.2 g. of uranium containing 7 g. of plutonium per given below in Table VII.

TABLE VII Section Ura- Pluto- Rare Sr Ru Cs Te Nb Zr Total Totalsl nium nium Earths Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent outer skin. 0. 9 1.1 46. 7 31. 1 0. 6 24. 2 28. a 14. 0 29. 2 45. 15. 2 Middle skin- 1.0 0. 9 27.2 0.9 19.0 6.1 9. 8 10.5 6.8 Inner skin--- 3.2 2.8 3.9 27.2 3.2 15.0 21.6 5.7 14.0 6.0 5.4 Interior. 95.2 82.8 20.2 16.8 94.1 18.3 17.3 74 s 42.5 25.1 47.1

y Here again it is obvious that extraction for minutes ton and cooled for 321 days was melted in an alumina is less complete than extraction carried out for 4 hours crucible under the same conditions as were prevailing in (Example III); this is particularly true in regard to stron- Example III; the ingot obtained was skinned three times.V tlum, tellurium and zirconium. The analytical results are compiled in Table V. Several runs were carried Vout Y1n which the tempera- TABLE V Section Ura- Pluto- Rare Sr Ru Gs Te Nb Zr Total Totaly nium nium Earths Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Outer skin. 1 5 1 6 44. 85. 41.

35 0 92. 6 13.8 o o g s 2 Middle Skin- 1. 6 1. 5 10. 8 0. 8 15. Inner Skin--. 3. 1 2. 8 0. 0 0. 0 3.1 0.0 0. 2 2. 3 0. 4 0.2 1. 8 Interior.. 93. 8 83. 4 1 8 0 3 86. 3 1. 3 7. 3 69. 9 12. 2 9. 1 54. 3

The extraction ofthe fission products into the skin ture of 1200 C. was maintained for 1l hours; this addiwas substantial. tional heating time did not significantly improve the ex- While all these previous examples were carried out by traction obtained after 4 hours.

melting for four hours at 1200 C., some tests were run The following example illustrates the separation of using a 30minute period only for the melting. This was the oxide layer from the uranium metal by mechanical true for Example V, which is comparable with Example I, means, namely, by draining the molten metal from an both using urania crucibles and temperatures of 1200 C. 55 opening in the bottom of the crucible.

Example V Example VII A thoria crucible was used which had an opening in the bottom; the opening could be closed by a stopper. 263.3 g. of neutron-bombarded uranium which contained 42 g. of plutonium per ton and had been cooled for a period of 298 days were melted for 4 hours at 1200 C. After melting the stopper was lifted and the metal cast from the bottom of the crucible into a tantalum 30 minutes did Ilot brlllg about 3S good an eXtfaCtlOn 0f container; a skull was retained in the thoria crucible.

tho SSoIl Products as Was obtained When-th 'tempera- 65 The analyses of skull and ingot cast in the tantalum A disk of uranium which contained 7 g. of plutonium per ton, weighed A30.6 g. vand had been cooled for 314 days, Was Amelted in a urania crucible, and the ingot was skinned once. The concentrations in the skin solution and the solution obtained from the interiorv metal are Skin 77 69 3 Inter10r...; 97. 2 96. 6 10.3 11.8 10. 6 80. 6 12.9 16. 2 8l. 0 34. 8 18. 2

ture of 1200` C. was upheld for four hours. container are given in Table VIII.

TABLE VI Section Ura- Pluto- Rare Ce Sr Ru Cs Te Nb Zr Total Total y nium nium Earths Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent 2.8 7.2 73.4 80.6 85.7 2.2 56.4 .1 55.9 27.9

TABLE VIII Section Ura- Pluto- Rare Sr Ru Cs Te Nb Zr Total Total y nium nlum Earths Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Percent Skull 2. 2.0 64. 0 42. 1 1.6 6.0 72. 5 9.2 38. 3 50. 9 18.3 Ingot 97. 6 88. 4 3. 1 0. 2 85. 2 O. 1 14. 5 1 9. 3 39. 7 9. 3 21.7

l Questionable value.

It will be noted that the cesium values in all of the experiments described above totaled considerably less than 100. In one experiment the crucible was leached and the solution obtained thereby was analyzed. It was found that the Crucible-leach solution contained 41.8% of the cesium. In the same experiment a' cold finger was suspended over the Crucible during melting; a cesium deposit was found thereon after the operation. This showed that a considerable amount of cesium is removed by volatilization and diifusion'into the Crucible.

Example VIII Then the eifect of various temperatures was examined. For this purpose two parallel experiments were carried out, one using a melting temperature of i200" C. and the other that of l310 C., both melting for four hours. In both instances the crucibles were made of aluminum oxide; they had been degassed, as were all the others and as was described previously. The uranium contained 67 g. of plutonium per ton. The analytical results are given in Table IX.

at 1395 C., is satisfactory. Another mixture which proved operative contained 42.74% calcium oxide, 44.19% aluminum oxide, 5.87% magnesium oxide, and 7.19% of lithium oxide. This mixture melts at between 1270 and 1280 C.

In the following an example is given which illustrates the embodiment of the invention using an oxide slag in the liquid state.

Example IX TABLE IX Charge, g. Section Uranium Pluto- Cs Sr Rare Te Zr Nb Ru Mo nium Earths 1,2004 hrs. In percent of content in starting material 116 1 Skin 2. 3 7. 8 15. 2 63. 9 70. 2 29.0 52.6 1. 7 1. 0

' Interior 97. 6` 88. 8 0. 2' 0. 2 0. 5 53. 5 46.1 99. 7 106 97 1,310 0.-4 hrs Chips 1. 8 7. 6 0.2 0. 5 15. 2 9.9 1. 9 0.0 0.2

131.9 Skin 2.0 2.1 2.9 17.6 31. 3 16. 2 41.0 0.3 1. 5

Interior 97. 6 84. 9 0. 03 0. 01 0. 7 76. 8 53. 7 89. 8 Y 102 94 This experiment shows that the fission products content of the interior is lower and that thus decontamination is better at 1310 C. than at 1200 C.

It was also found that decontamination of the uranium and its separation from ssion products is furthermore improved by providing for a fluid slag instead of the solid slag produced in the experiments of the preceding examples. This can be accomplished satisfactorily by adding to at least one oxide of this invention several oxides, such as lithium oxide, the oxides of alkaline earths, 4-f type rare earths, beryllium, and/or of zirconium in proportions to obtain a slag mixture that melts between 1200 and 1400 C. As a result of the uidity of the slag the layer of the slag at the reaction interface is constantly renewed by the action of the more rapid diffusion in a liquid as compared with that in a solid. When the uranium has been suiiiciently decontaminated the melt is cooled until the slag is solidified but the uranium still is in the liquid state, and the uranium is then poured oli the solid slag. Oxide mixtures which have been found operative for the process Vare the CaO-MgO-Al203 eutectics (41.5-6.751.8%

and 46.0-6.3-47.7%, respectively) which melt atabout l345 C. Also the binary eutectic containing 50% calcium oxide and aluminum oxide, which melts So was the skull retained in the graphite Crucible. The results are computed in Table X.

TABLE X Skull, Ingot, percent percent Uranium 16. 6 82. 8 P1utonium 13.3 80.7 Rare Earths 64. 8 24. 1 Strontium 88. 7 0. 8 Ruthenium 11. 4 89. 4 Cesium.-- 46. 8 0. 9 Tellurium.. 7. 6 2. 2 Niobium... 13. 2 68. 7 Zireoniurn 71.8 y 10.7

lt will be understood that this invention is not to be limited to the details given herein but that it may be modified within the scope of the appended claims.

What is claimed is:

1. A process of removing fission products from neutronbombarded uranium comprising melting said uranium in contact with at least one refractory oxide selected from the group consisting of uranium dioxide, thorium oxide, magnesium oxide, beryllium oxide and aluminum oxide assaeeo whereby a slag layer forms, and separating the fission products-enriched slag layer from a uranium layer.

2. The process of claim l wherein melting is carried out in an inert atmosphere.

3. The process of claim 2 in which the inert atmosphere is helium.

`4. The process of claim 1 in which melting is carried out between 1150 and 1400 C.

5. The process of claim 4 wherein the melting temperature is between 1250 and 1400 C. and the oxide iS chosen so that it is liquid at said temperature.

6. The process of claim 4 wherein the temperature is between 1150 and 1250 C. and the oxide is solid at 'said temperature.

7. The process of claim 6 in which the oxide is used in the form of a crucible and the melting is carried out in said Crucible.

8. The process of removing fission products from neutron-bombarded uranium comprising adding a refractory oxide selected from the group consisting of uranium dioxide, thorium oxide, magnesium oxide and aluminum oxide to said uranium, said refractory oxide being mixed with at least one other oxide selected from the group consisting of lithium oxide, alkaline earth oxides, rare earth oxides, beryllium oxide and zirconium oxide in quantities to yield a slag that melts between 1250 and 1400 C.; heating the mixture of uranium and oxides until it melts; cooling the molten mass until an oxide slag has solidified but the uranium still is in liquid form; separating the uranium from the solid fission products-containing slag; and cooling the uranium until it is solid.

9. The process of claim 8 in which the oxide mixture is the eutectic of calcium oxide, magnesium oxide and aluminum oxide.

References Cited in the le of this patent Saul: Pyrochemical Separation Methods: III. The Removal of Fssion Products From Molten, Irradiated Uranium, by Solid Oxides, USAEC Document NAA- SR-l361, September 1, 1955, declassied January 12,

20 1956, 22 pages. 

1. A PROCESS OF REMOVING FISSION PRODUCTS FROM NEUTRONBOMBARDED URANIUM COMPRISING MELTING SAID URANIUM IN CONTACT WITH AT LEAST ONE REFRACTORY OXIDE SELECTED FROM THE GROUP CONSISTING OF URANIUM DIOXIDE, THORIUM OXIDE, MAGNESIUM OXIDE, BERYLLIUM OXIDE AND ALUMINUM OXIDE WHEREBY A SLAG LAYER FORMS, AND SEPARATING THE FISSION PRODUCTS-ENRICHED SLAG LAYER FROM A URANIUM LAYER. 